ethyl (Z,2S)-2-hydroxy-3-trimethylsilylhept-3-en-5-ynoate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl (Z,2S)-2-hydroxy-3-trimethylsilylhept-3-en-5-ynoate
• 化学式: C₁₂H₂₀O₃Si
• 分子量: 240.374
• InChiKey: UOTRUCDQHYABNF-DWOQACPDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.74
• 重原子数：
  16.0
• 可旋转键数：
  4.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  46.53
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  乙醛酸乙酯 、 1-trimethylsilyl-1,3-pentadiyne 在 bis(1,5-cyclooctadiene)rhodium(I) trifluoromethanesulfonate 、 氢气 、 (S)-(-)-5,5-二氯-6,6-二甲氧基-2,2-双(二苯基磷酸)-1,1-联苯基 作用下， 以 1,2-二氯乙烷 为溶剂， 40.0 ℃ 、100.0 kPa 条件下， 生成 、 ethyl (Z,2S)-2-hydroxy-3-trimethylsilylhept-3-en-5-ynoate
  参考文献：
  名称：

  α-Hydroxy Esters via Enantioselective Hydrogen-Mediated C−C Coupling:  Regiocontrolled Reactions of Silyl-Substituted 1,3-Diynes

  摘要：

  Catalytic hydrogenation of ethyl glyoxalate in the presence of 1,3-diynes 4a-9a using chirally modified rhodium catalysts enables formation of alpha-hydroxy esters 4c-9c in highly optically enriched form. Notably, for such trialkylsilyl-substituted 1,3-diynes, C-C coupling occurs exclusively at the carbon atom bearing silicon. pi-Back-bonding from low valent rhodium as described by the Dewar-Chatt-Duncanson model appears to direct the regiochemistry of C-C coupling, as corroborated by calculations of the diyne LUMO coefficients.

  DOI：

  10.1021/ol061485k

文献信息

• α-Hydroxy Esters via Enantioselective Hydrogen-Mediated C−C Coupling:  Regiocontrolled Reactions of Silyl-Substituted 1,3-Diynes
  作者：Chang-Woo Cho、Michael J. Krische

  DOI：10.1021/ol061485k

  日期：2006.8.1

  Catalytic hydrogenation of ethyl glyoxalate in the presence of 1,3-diynes 4a-9a using chirally modified rhodium catalysts enables formation of alpha-hydroxy esters 4c-9c in highly optically enriched form. Notably, for such trialkylsilyl-substituted 1,3-diynes, C-C coupling occurs exclusively at the carbon atom bearing silicon. pi-Back-bonding from low valent rhodium as described by the Dewar-Chatt-Duncanson model appears to direct the regiochemistry of C-C coupling, as corroborated by calculations of the diyne LUMO coefficients.